Assessing The Safety Of Lithium-Ion Batteries | February 11, 2013 Issue - Vol. 91 Issue 6 | Chemical & Engineering News
 
 
7
Facebook
Volume 91 Issue 6 | pp. 33-37
Issue Date: February 11, 2013

Assessing The Safety Of Lithium-Ion Batteries

Airplane fires refocus attention on rare but serious battery hazards and ways to avoid them
Department: Science & Technology
Keywords: lithium-ion battery, 787, battery fire, battery safey, electrode
[+]Enlarge
EVIDENCE
An NTSB investigator examines a Boeing 787 electronics bay where a Li-ion battery caught fire as the empty plane sat on the ground at Boston’s Logan International Airport.
Credit: NTSB
09106-scitech1-NTSBInvestigatorcxd
 
EVIDENCE
An NTSB investigator examines a Boeing 787 electronics bay where a Li-ion battery caught fire as the empty plane sat on the ground at Boston’s Logan International Airport.
Credit: NTSB

Lithium-ion batteries are back in the crosshairs after two safety incidents aboard Boeing 787 Dreamliner airplanes in January. Headlines everywhere drew readers to stories about flaming and smoldering batteries. Reports warned of these popular power packs’ tendency to overheat and burst into flames. Broadcasts pointed out that fires in portable electronic devices several years ago prompted manufacturers to recall millions of Li-ion laptop batteries.

But these batteries are statistically very reliable. “There’s a lot of mythology in the area of lithium-ion battery safety,” says Brian M. Barnett, a battery safety specialist at Lexington, Mass.-based technology development firm Tiax. Failure rates for rechargeable Li-ion batteries are on the order of one in 10 million cells, he says. “That’s not a reliability problem. It’s an exception.”

Yet exceptions can still be dangerous. As a result of the enormous number of Li-ion cells manufactured each year—about 4 billion in 2012, according to Barnett—some of those failures can lead to fires and serious safety incidents. Although the probability is tiny, the potential for mishap grows as Li-ion battery use surges. Adding to the concern is the scale issue. Li-ion batteries range from palm-sized or smaller packs weighing an ounce or less to 400-plus-lb electric vehicle batteries, and the larger devices can cause more serious problems if they fail.

[+]Enlarge
BURNED
This Boeing 787 Li-ion battery caught fire while the empty plane was grounded at Boston’s Logan International Airport.
Credit: NTSB
09106-scitech1-batterycxd
 
BURNED
This Boeing 787 Li-ion battery caught fire while the empty plane was grounded at Boston’s Logan International Airport.
Credit: NTSB

Many batteries already feature fuselike structures and several other built-in safety devices. Yet scientists and engineers are working on broader safety strategies that address the characteristics of nearly every battery component. Researchers are tailoring the physical, chemical, electrical, and other properties of the positive and negative electrodes and the materials that electrically insulate them to make them less reactive. They are studying ways to reduce the flammability of the electrolyte solution that carries lithium ions through the battery. And they are designing robust battery management systems that monitor a wide range of battery performance and operating parameters to provide early warning of potential danger.

Khalil Amine, manager of Argonne National Laboratory’s Advanced Lithium Battery Technology group, explains that a broad approach is necessary because “safety must be addressed at the full system level.”

[+]Enlarge
SAY HELLO
A cell phone battery typically weighs a few ounces.
Credit: Shutterstock
09106-scitech1-cellphonecxd
 
SAY HELLO
A cell phone battery typically weighs a few ounces.
Credit: Shutterstock

Li-ion batteries’ knack for packing more energy into smaller, lighter units than other common batteries has spurred enormous growth in Li-ion use. Batteries based on this type of chemistry power most of today’s cell phones, tablets, laptops, and other portable electronic devices. In the past several years, they have become popular among manufacturers of power tools and other high-current equipment. The low weight and high energy density also make Li-ion batteries attractive for use in hybrid-electric city buses and several lines of electric and hybrid-electric passenger cars. For the same reasons, Boeing chose the batteries for its fuel-efficient Dreamliners.

A potential shortcoming of Li-ion batteries is their flammable electrolyte solutions. Unlike other common types of batteries, in which the electrolytes consist of aqueous solutions of acid or base, the electrolyte in Li-ion cells typically consists of lithium salts in flammable organic solvents such as ethylene carbonate and ethyl methyl carbonate.

[+]Enlarge
PORTABLE
A laptop battery usually weighs around 1 lb.
Credit: Shutterstock
09106-scitech1-laptopcxd
 
PORTABLE
A laptop battery usually weighs around 1 lb.
Credit: Shutterstock

Under normal operation, charging the battery causes lithium ions in the electrolyte solution to migrate from the cathode through a micrometer-thin porous polymer separator and insert themselves (intercalate) in the anode. Common cathodes are based on LiCoO2, LiMn2O4, LiFePO4, and related oxides. The anode is generally a form of graphite. Charge-balancing electrons also move to the anode but travel through an external circuit in the charger. On discharge, meaning when the battery is used to provide power, the reverse process occurs, and electrons flow through the device being energized.

In rare circumstances, some process could internally or externally short-circuit the battery or subject it to abusive electrical conditions or other trauma. According to Daniel H. Doughty of Battery Safety Consulting in Albuquerque, N.M., those events could generate a lot of heat inside the cell, ignite the liquid, or rapidly raise its vapor pressure until the cell bursts.

[+]Enlarge
INNER WORKINGS
A similar set of electricity-generating chemical reactions underlie Li-ion battery operation, regardless of cell size. However, failures in the larger units can be particularly hazardous.
09106-scitech1-batterydia
 
INNER WORKINGS
A similar set of electricity-generating chemical reactions underlie Li-ion battery operation, regardless of cell size. However, failures in the larger units can be particularly hazardous.

In one case in 2011, a battery-powered Chevy Volt car that had been subjected to a severe side-impact and rollover crash test caught fire during subsequent testing several weeks later. The National Highway Traffic Safety Administration found that the fire was likely caused by a coolant leak and minor battery puncture that occurred during the earlier crash test. The agency concluded that electric cars do not pose a greater risk of fire than gasoline-powered vehicles. And General Motors modified the car’s design, adding structural reinforcement to better protect the battery pack from damage.

The airplane events involved 63-lb battery units on 787s operated by Japan Airlines (JAL) and All Nippon Airways (ANA). The JAL battery burned as the empty plane sat on the tarmac at Boston’s Logan International Airport. The ANA battery smoldered in flight, causing the pilots to make an emergency landing in central Japan. The U.S. National Transportation Safety Board (NTSB) and the Japan Transport Safety Board, respectively, ruled out excess voltage as the cause of the JAL and ANA fires. As of C&EN’s press time, the causes of the problems remain unknown and the investigations continue.

[+]Enlarge
SKY HIGH
The Boeing 787 auxiliary power unit battery weighs 63 lb.
Credit: Boeing
09106-scitech1-boeingcxd
 
SKY HIGH
The Boeing 787 auxiliary power unit battery weighs 63 lb.
Credit: Boeing

Hazardous battery failure, including fires, can be triggered by a number of factors. For example, micrometer-sized metal particles generated during cutting, pressing, grinding, and other manufacturing steps could contaminate the cells. The particles could accumulate and eventually form a short circuit—a conductive contact between the anode and cathode. According to Barnett, experienced manufacturers today use scrupulously clean methods that minimize contamination and therefore that mode of failure.

Overcharging a battery or exposing it to too high voltage by using the wrong charger or one that failed can push the cathode to an unsafe oxidizing state. Doughty explains that under those conditions, the cathode can react with and decompose the electrolyte solution, generating heat and reactive gases such as hydrocarbons. The gases can react further with the cathode, liberating more heat and triggering thermal runaway—uncontrollable heating that can destroy a battery violently.

[+]Enlarge
PLUG-IN CAR
The battery in the electric car Chevy Volt weighs roughly 435 lb.
Credit: Shutterstock
09106-scitech1-chevyvoltcxd
 
PLUG-IN CAR
The battery in the electric car Chevy Volt weighs roughly 435 lb.
Credit: Shutterstock

Overcharging can also drive more lithium from the cathode than can be accommodated via intercalation in the graphite lattice. In that scenario, lithium metal can accumulate (plate) on the anode surface, making it dangerously reactive.

The process could also generate lithium dendrites that grow through microscopic pores in the separator and bring the electrodes into direct electrical contact. That short circuit can cause the cells to discharge rapidly and generate a lot of heat.

Choosing a safe cathode is one key aspect of battery construction. But there are trade-offs. LiCoO2 cathodes developed in the early 1990s made Li-ion batteries the commercial success they are today. That material remains popular for consumer electronics because it provides relatively high charge capacity. Yet it is less stable than other cathode materials. At elevated temperatures, LiCoO2 liberates oxygen, which can react with organic cell ­components.

LiMn2O4 tolerates heat better than LiCoO2, but the manganese-based material’s charge capacity is lower, and it too decomposes at high temperature. In contrast, LiFePO4 stands up especially well to thermal abuse due to the strength of phosphorus-oxygen bonds, Amine says. But the operating voltage and energy density on a volume basis are lower than those of LiCoO2.

The film separating the electrodes measures just a few tens of micrometers, but it also can be engineered for cell safety in some applications. Christopher J. Orendorff, a battery safety specialist at Sandia National Laboratories, explains that sandwiching a layer of polyethylene between two layers of polypropylene can provide a degree of protection against mild overheating.

Here’s how it works: If the temperature in the cell should start to approach 135 °C, the melting point of polyethylene, that polymer will begin to melt and plug the pores of polypropylene, which has a roughly 30 °C higher melting point. Under favorable conditions, the separator’s plugged pores block Li-ion diffusion, which shuts down the cell, letting it cool safely.

[+]Enlarge
SAFETY SPHERES
As the Li-ion battery temperature starts to rise dangerously, these polyethylene spheres (the largest in this SEM image is ~17 μm in diameter) melt and coat the electrode or separator on which they are deposited. The process blocks ion transport and shuts down the hot battery.
Credit: Adv. Energy Mater.
09106-scitech1-PEpherescxd
 
SAFETY SPHERES
As the Li-ion battery temperature starts to rise dangerously, these polyethylene spheres (the largest in this SEM image is ~17 μm in diameter) melt and coat the electrode or separator on which they are deposited. The process blocks ion transport and shuts down the hot battery.
Credit: Adv. Energy Mater.

To extend the thermal protection range to temperatures above 135 °C, some researchers are working with higher melting point polymers such as polyimides. Entek Membranes, in Lebanon, Ore., follows a similar strategy, embedding a ceramic layer in ultra-high-molecular-weight polyethylene to form a robust higher melting point composite.

Melting-induced material changes lie at the heart of another battery safety innovation. Marta Baginska, Jeffrey S. Moore, Scott R. White, and coworkers at the University of Illinois, Urbana-Champaign, fabricate batteries with embedded microspheres of polyethylene and paraffin wax. Test results from batteries with microsphere-coated anodes and separators show that as the temperature inside the cell approaches the spheres’ melting point, the molten material flows and coats the battery surfaces. That response, which the team exploits in related work to make self-healing materials, forms an insulating barrier that shuts down the battery (Adv. Energy Mater., DOI: 10.1002/aenm.201100683).

Formulating electrolyte solutions with phosphates and phosphazenes can reduce flammability. These radical scavengers terminate radical-based combustion reactions, thereby preventing fires. But evaluating the effectiveness of these compounds in realistic battery-failure tests remains challenging. Furthermore, in some cases these additives reduce battery output.

Going a step further, researchers in several labs are studying nonvolatile, nonflammable ionic liquids, fluoroethers, and other highly fluorinated solvents as Li-ion battery electrolytes. The winning solution has not yet emerged from these ongoing studies.

Along the same lines, other researchers are studying Li-ion batteries that contain no liquids at all. These solid-state batteries, which contain inorganic lithium-ion conductors, are inherently nonflammable. According to Ji-Guang (Jason) Zhang of Pacific Northwest National Laboratory, this type of Li-ion battery is very stable and safe and exhibits long cycle life and shelf life. The key drawback is that these cells need to be fabricated via labor-intensive vacuum deposition methods, which are costly.

[+]Enlarge
ASSEMBLY REQUIRED
Argonne’s Andrew Jansen loads test electrodes (in his hands) into an instrument that couples electrodes and separator film (long white ribbon) for making commercial cell-phone-style Li-ion batteries.
Credit: Mitch Jacoby/C&EN
09106-scitech1-LiIonCellAssemblycxd
 
ASSEMBLY REQUIRED
Argonne’s Andrew Jansen loads test electrodes (in his hands) into an instrument that couples electrodes and separator film (long white ribbon) for making commercial cell-phone-style Li-ion batteries.
Credit: Mitch Jacoby/C&EN

Protection against overcharging can come in the form of molecules that happily flip-flop electrochemically at a given potential. These so-called redox shuttles, which were first studied decades ago, bounce back and forth readily between oxidized and reduced states at a potential slightly higher than the battery’s end-of-charge point.

If the battery charger tries to push the battery beyond that point, that energy is taken up by the shuttles. “They trick the battery and prevent it from being overcharged,” Amine says. As long as the shuttles are stable, the battery holds steady at the shuttle’s potential. Amine, Zhengcheng Zhang, and Argonne colleagues have evaluated several shuttles including a bis-meth­oxyethoxy benzene compound designed via quantum calculations. The compound is fully compatible with Li-ion cells and remained stable throughout a 180-shuttle-cycle test (Energy Environ. Sci., DOI: 10.1039/c2ee21977h).

Working in parallel with researchers who focus on the chemistry and materials science issues are others who are designing ever more reliable battery management electronics. Barnett and colleagues at Tiax have developed a sensor system and algorithm that detect changes in battery performance that may signal onset of the early stages of an internal short—a traditionally undetectable situation. He explains that this detection system could be coupled to a control system in an automobile that activates a service maintenance light, broadcasts a warning message, or in an extreme case, disables the battery.

These features are not going to appear in Li-ion batteries tomorrow. As battery specialists point out, new battery designs and materials need to be thoroughly tested under hazardous abuse conditions to properly assess their safety benefits. In addition, those safety-enhancing features cannot reduce the battery’s performance and power output.

Meanwhile, NTSB investigators working on the JAL 787 case continue combing through electrical- and mass-measurement data and various types of imaging results, searching for the cause of the battery fire. “We know the world is waiting for these results and we are working hard to get them,” says NTSB spokesman Peter Knudson. “We are making progress. It’s taking some time, but it’s important we get it right.” Knudson adds that the agency will soon issue safety recommendations based on its findings.

The advanced state of today’s Li-ion battery safety and the broad push to drive safety to even higher levels leaves Battery Safety’s Doughty upbeat about the battery’s transportation prospects. “I’m bullish on Li-ion batteries for electric vehicles,” Doughty says, “provided the required safety analysis is completed rigorously.”

 
Chemical & Engineering News
ISSN 0009-2347
Copyright © American Chemical Society
Comments
John Van Allen  (February 13, 2013 8:24 AM)
Being an electronics engineering technician who resides in a 3rd world country where, due to necessity, we make very effort to repair things instead of throwing them away like up north I have accumulated several Li-Ion battery packs in my repair shop. The latest repair attempt was on a portable oxygen generator that an ailing friend of mine owned. He had left it without charging for too long and the individual cell voltages which are normally around 3.6VDC had dropped below 50% of this. The battery pack, a 14.8V 4.0Ah unit, has a circuit board built into it which incorporates an electronic shut down mechanism. I am aware of the dangers inherent in Li-Ion batteries so using great care I removed the battery pack from the unit and carefully bypassed the electronics then used a precision HP adjustable lab power supply I carefully recharged the cells using a criteria of a maximum current of .2C and a maximum voltage of 4.2VPC. I had to start at a low voltage and gradually raise it never going above .2C (800ma)while watching for any heating. The cells stayed cool throughout the recharge and in about 8 hours they were fully charged. I then re-installed the pack into the unit but the circuit still refused to connect the battery pack to the load. Talking with the factory they said that the circuit board had performed an "irreversable shut down" and I needed to buy a new battery to the tune of 230 USD! The battery is on order now. Just out of curiosity I decided to perform a controlled discharge test on the battery and it performed excellently giving me 4.1Ahrs, better than new! So now I have a perfectly good Li-Ion battery which I must throw away because a smart chip in a circuit board will not allow me to reset its decision to erroneously shut down a perfect pack.

I have several battery packs like the one mentioned above in my lab now. The one mentioned above has a label ULTRALIFE S/N: 05861109DN and it is used in an AirSep Corporation Oxygen Concentrator.

The AirSep technicians are the only ones I could contact about this. I cannot locate ULTRALIFE in web searches.

I am thinking about re-using these perfectly good (and expensive) batteries in personal projects but the charging process I am using now is a bit limiting and cumbersome. I wonder if others have addressed this issue? If so I would like to hear from you.
Best Regards
John
Henri Barten  (April 5, 2013 6:59 AM)
As per John van Allen's comment, working for a company that sells Li-Ion battery packs with the equipment we sell, I can confirm that 9 out 10 times, it's the circuitry that fails, and the cells are ok. It's not uncommon that if you charge the cells your self that get more capacity, and we often do that by design for safety. Unfortunately due to the strict regulations that limits 'tampering' with defective batteries, globally tons off battery cells must be ending up in our chemical waste bin's. It would be a good for the environment and employment, if cells would be tested and re-used, or the circuitry could be easily (modular) replaced, without infringing the safety. Only legislation can force manufacturers to do so, but I guess that's will remain on the bottom of our environmental wishlist for a while.
Henri Barten  (April 5, 2013 8:43 AM)
John, the most likely root cause of failing batteries has to do with the fact Cell
designers have developed mechanical charge interrupt devices (CIDs) for cylindrical cells used in consumer electronic devices. On activation, CIDs physically and irreversibly disconnect the cell from the circuit. Although CIDs are usually described as overcharge protection devices, they will activate if anything causes cell internal pressure to exceed the activation limit. This could include overcharge, cell overheating, significant lithium plating followed by electrolyte breakdown, mild internal shorting, and/or significant cell over-discharge.
Lee Kresge  (February 13, 2013 4:43 PM)
Remote control vehicle enthusiasts have been beating the living daylights out of rechargeable batteries for decades. A LOT was learned about NiCad's back in the day at the expense and with the support of hobbyists. Then, the same was done for NiMH chemistry. Now, with higher capacity and lower weight, LiPo and LiFe batteries are being gobbled up in huge quantities. Now that we know what we are doing, our rate of battery related fires and explosions are extremely low. Perhaps the NTSB and the battery manufacturers should hire, or at least consult with, some of us putting these expensive/high performance batteries in our toys. They can start wit me if they'd like.
Leave A Comment